WO1984000982A1 - Recompression process - Google Patents

Recompression process

Info

Publication number
WO1984000982A1
WO1984000982A1 PCT/CH1983/000100 CH8300100W WO8400982A1 WO 1984000982 A1 WO1984000982 A1 WO 1984000982A1 CH 8300100 W CH8300100 W CH 8300100W WO 8400982 A1 WO8400982 A1 WO 8400982A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluoride
nickel salt
solution
salts
agent
Prior art date
Application number
PCT/CH1983/000100
Other languages
German (de)
French (fr)
Inventor
Edgar Grueninger
Original Assignee
Ffa Flug Fahrzeugwerke Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ffa Flug Fahrzeugwerke Ag filed Critical Ffa Flug Fahrzeugwerke Ag
Priority to DE8383902690T priority Critical patent/DE3374791D1/en
Priority to AT83902690T priority patent/ATE31198T1/en
Priority to AU18861/83A priority patent/AU1886183A/en
Publication of WO1984000982A1 publication Critical patent/WO1984000982A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers

Definitions

  • a common feature of all anodic oxidation processes is that the surfaces obtained, whether colorless or colored in one or more stages, are resistant to contact and are sensitive to corrosive substances.
  • various post-compaction processes so-called seal processes, have been developed, through which a contact and corrosion-resistant surface is obtained.
  • the most common of these post-compression processes is treatment with boiling water or steam, known as hot water and steam sealing. These processes require very high energy consumption.
  • Another disadvantage of hot water treatment is the formation of an undesirable deposit of lime and other salts and impurities dissolved in the bath water, which must then be removed mechanically in an additional operation.
  • sealants have been proposed which are generally based on high-molecular compounds, but which in turn make the process more expensive because they have to be supplemented.
  • Metal salts such as nickel salts, for example nickel acetate, have also already been proposed as an addition to the hot water baths in order to intensify the deformation.
  • the compression effect of these salt baths already occurs at a temperature of 70 ° C, so it does not require a boiling temperature, but a very strong one also forms here Rubber that cannot be left on the surface.
  • seal baths known hitherto Another difficulty of the seal baths known hitherto is that they usually have a lifespan of about 3 to 6 weeks. After this time they are unusable and must be thrown away.
  • the present invention therefore relates to a process for the recompression of anodically oxidized, undyed or colored metal surfaces, in particular aluminum surfaces, which is characterized in that the still wet surface is treated at a temperature below 30 ° C. with an aqueous solution which contains at least one nickel salt and contains at least one fluoride.
  • Suitable nickel salts are inorganic nickel salts, such as nickel chloride, sulfate, carbonate, nitrate, etc., and also organic nickel salts, such as nickel acetate and others.
  • the fluoride is preferably a fluoride of an alkali metal salt, such as sodium fluoride, potassium fluoride, etc., or of ammonium, for example (NH. HF 2 , or an organic fluoride.
  • the salts are preferably used in approximately stoichiometric proportions of nickel salt to fluoride, the crystal water present also having to be taken into account in the case of the nickel salt. Larger or smaller amounts of the nickel or fluoride salt can also be used, but the results are generally less good.
  • the optimal addition of salts per liter of bath liquid depends on the surface to be treated and can be determined by simple tests. In general, the total salt state (nickel salt and fluoride) is about 1 to 20 g / liter, with an amount of about 10 g / liter being preferred for aluminum surfaces.
  • the pH of the treatment solution is advantageously in the slightly acidic range, e.g. at 5.5 to 5.8 and can be mixed with a common acid e.g. Acetic acid.
  • the treatment takes place at a temperature below 30 ° C, preferably at room temperature, which can drastically reduce energy consumption.
  • the contact time of the salt solution with the metal surface is not critical. Generally it is at least about 10 minutes.
  • Treatment can be by immersion in a seal bath or by spraying, brushing or in any way.
  • the treated surface is generally rinsed off with cold water after the treatment, but this rinse can easily be omitted without having an adverse effect on the quality of the surface.
  • a preservative is recommended, as is also common for dye baths and other galvanic baths, for example, formalin, "Preventol" and others; in general an addition of 0.01 g / liter is sufficient.
  • the preservative is not water-soluble, it can be added to the aqueous seal solution dissolved in a water-miscible solvent, for example a lower aliphatic alcohol, such as methanol, ethanol, propanol, n- or iso-butanol, etc.
  • a water-miscible solvent for example a lower aliphatic alcohol, such as methanol, ethanol, propanol, n- or iso-butanol, etc.
  • Such an additive can also be recommended for solutions for spraying, brushing, etc., if these solutions are kept open for a long time, since they can easily be contaminated by microorganisms.
  • the seal solutions can contain other conventional additives, such as wetting agents and the like.
  • the surfaces to be treated are subjected to the seal treatment according to the invention while still wet, ie practically immediately after the oxidation or coloring or after the last rinse.
  • the method according to the invention gives the desired ones no more compaction, even if the surface is wetted again. This is in contrast to the previous hot sealing processes, in which the surface can still be compacted in the dry state even after long storage.
  • the method according to the invention results in excellent corrosion resistance and a smooth, attractive appearance of the surface.
  • the compression effect has e.g. aluminum generally reaches its maximum after 24 hours.
  • the treated objects have a permanent corrosion resistance and are suitable for all common uses. No deposits or hydrate formation are observed on the surfaces.
  • the removal rate for aluminum sheet is determined by
  • ISO 3210 which may be up to 30 mg / dm 2 in hot compression according to the currently applicable Euras standard, is around 7 to 10 mg / cm 2 for cold-compressed sheets according to the invention.
  • the removal values obtained are both compared to those of colorless anodized aluminum surfaces and in particular of aluminum surfaces colored, for example, with electrolytic metal salt staining hot-compressed surfaces (with or without added salt) significantly improved.
  • the solutions used according to the invention have the advantage of being significantly less polluting than the previous ones, since their service life is practically unlimited, so they do not have to be thrown away.
  • Another object of the present invention is a commercial agent for performing the above cold sealing process.
  • This agent is characterized by a content of at least one nickel salt and at least one fluoride of the type described above.
  • the agent can be present as a dry mixture, as a paste or as a concentrate. It preferably contains the salts in an approximately stoichiometric ratio of nickel salt. H 2 O to fluoride.
  • the agent may already contain other additives such as wetting agents, preservatives, etc., but these can also be added separately when preparing the solution.
  • the agent has an unlimited shelf life and can be packaged, for example, in such a dosage form that weighing, measurement or the like is no longer necessary when preparing the solution or supplementing it. example 1
  • a bath is made by dissolving 10 g / liter of a mixture of 262.9 g of Ni (SO 4 ). 6H 2 O and 42.0 g NaF in water. 0.5 g / liter of the wetting agent "Ekalin F" (Sandoz) and 0.01 g / liter "Preventol” (Bayer), dissolved in 10 g / liter of butanol, are added to this solution and the pH of the solution to 5 with acetic acid. 6 set.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

Anodized metal surfaces are cold pressed while they are treated at a temperature lower than 30oC in a still wet state with an aqeous solution containing nickel salt and at least one fluoride. The solution may contain further additives for example a preservating agent, optionally dissolved in a solubilization agent such as alcohols.

Description

Nachverdichtungsverfahren Post-compaction process
Beim bekannten anodischen Oxidieren von Metalloberflächen, insbesondere solchen aus Leichtmetallen, wie z.B. Aluminium, durch Umwandlung der obersten Metallschichten entstehen Schutzschichten aus dem entsprechenden Metalloxid. Hierbei entstehen feinporige Ueberzüge, die sich für Reaktionen mit verschiedenen Reagentien und/ oder Farbstoffen eignen, die es heute ermöglichen, insbesondere Aluminiumoberflächen in einer grossen Anzahl Farbtöne einzufärben. Je nach dem Verwendungszweck dieser als "eloxierte" Aluminiumgegenstände bekannte Produkte im Innen- oder Ausseneinsatz werden mehr oder weniger wetterfeste Oberflächen benötigt. Die diversen hierfür geeigneten Färbemittel und deren Anwendung sind dem Fachmann bestens bekannt und benötigen hier keiner näheren Erläuterung.In the known anodic oxidation of metal surfaces, especially those made of light metals, such as Aluminum, by converting the top metal layers, protective layers are created from the corresponding metal oxide. This produces fine-pore coatings that are suitable for reactions with various reagents and / or dyes, which today make it possible to dye aluminum surfaces in particular in a large number of colors. Depending on the intended use of these products, known as "anodized" aluminum objects, for indoor or outdoor use, more or less weatherproof surfaces are required. The various colorants suitable for this and their use are well known to the person skilled in the art and do not require any further explanation here.
Allen anodischen Oxidationsverfahren ist gemeinsam, dass die erhaltenen Oberflächen, ob färblos oder in einer oder mehreren Stufen gefärbt, gegen Berührung und gegen korrodierende Substanzen empfindlich sind. Um diesen grossen Nachteil zu beheben, wurden verschiedene Nachverdichtungsverfahren, sogenannte Sealverfahren, entwickelt, durch welche eine berührungs- und korrosionsfeste Oberfläche erhalten wird. Das gebräuchlichste dieser Nachverdichtungsverfahren ist eine Behandlung mit kochendem Wasser oder Dampf, bekannt als Heisswasser- und Dampf sealing. Diese Verfahren erfordern einen sehr hohen Energieverbrauch. Ein weiterer Nachteil der Heisswasser behandlung ist die Bildung einer unerwünschten Ablagerung aus Kalk und anderen im Badwasser gelösten Salzen und Verunreinigungen, welche anschliessend in einem zusätzlichen Arbeitsgang mechanisch entfernt werden muss. Zur Verhinderung solcher Ablagerungen wurden sogenannte Sealhilfsmittel vorgeschlagen, die im allgemeinen auf der Basis hochmolekularer Verbindungen aufgebaut sind, das Verfahren jedoch wiederum verteuern, da sie ergänzt werden müssen.A common feature of all anodic oxidation processes is that the surfaces obtained, whether colorless or colored in one or more stages, are resistant to contact and are sensitive to corrosive substances. In order to remedy this major disadvantage, various post-compaction processes, so-called seal processes, have been developed, through which a contact and corrosion-resistant surface is obtained. The most common of these post-compression processes is treatment with boiling water or steam, known as hot water and steam sealing. These processes require very high energy consumption. Another disadvantage of hot water treatment is the formation of an undesirable deposit of lime and other salts and impurities dissolved in the bath water, which must then be removed mechanically in an additional operation. To prevent such deposits, so-called sealants have been proposed which are generally based on high-molecular compounds, but which in turn make the process more expensive because they have to be supplemented.
Auch Metallsalze, wie Nickelsalze, z.B. Nickelacetat, wurden als Zusatz zu den Heisswasserbädern bereits vorgeschlagen, um die Verichtung noch zu verstärken. Die Verdichtungswirkung dieser Salzbäder tritt bereits bei einer Temperatur von 70°C ein, erfordert also keine Siedetemperatur, doch bildet sich auch hier ein sehr starker Belag, der nicht auf der Oberfläche belassen werden kann.Metal salts, such as nickel salts, for example nickel acetate, have also already been proposed as an addition to the hot water baths in order to intensify the deformation. The compression effect of these salt baths already occurs at a temperature of 70 ° C, so it does not require a boiling temperature, but a very strong one also forms here Rubber that cannot be left on the surface.
Ein weiterer Nachteil der bisher vorgeschlagenen Sealverfahren besteht ferner darin, dass bereits ein höherer Gehalt an Silikaten, Phosphaten, Chloriden und dergleichen im Wasser als "Sealgift" wirkt, d.h. es entstehen Schichten ungenügender Qualität, die im Salztest sehr rasch abgebaut werden und durchkorrodieren.Another disadvantage of the sealing processes proposed so far is that a higher content of silicates, phosphates, chlorides and the like in water acts as a "seal poison", i.e. Layers of insufficient quality are formed, which are broken down very quickly in the salt test and corrode completely.
Eine weitere Schwierigkeit der bisher bekannten Sealbäder besteht ferner darin, dass sie üblicherweise eine Lebensdauer von etwa 3 bis 6 Wochen aufweisen. Nach dieser Zeit sind sie unbrauchbar und müssen weggeworfen werden.Another difficulty of the seal baths known hitherto is that they usually have a lifespan of about 3 to 6 weeks. After this time they are unusable and must be thrown away.
Es wurde nun ein neues Seälverfahren entwickelt, welches eine Behandlung bei Temperaturen unter 30°C und insbesondere auch bei Zimmertemperatur erlaubt, keine Badverunreinigung bewirkt, nur den Ersatz der durch das Behandlungsgut entfernten Badbestandteile aber keine Erneuerung des Bades benötigt und hervorragende Verdichtungen der Ueberzüge ergibt.A new seeling process has now been developed, which allows treatment at temperatures below 30 ° C and in particular also at room temperature, does not cause bath contamination, only requires replacement of the bath components removed by the material to be treated but no renewal of the bath and results in excellent compaction of the coatings.
Ueberraschenderweise wurde gefunden, dass sich diese Resultate durch Behandlung der anodisch oxidierten und gegebenenfalls gefärbten Metalloberflächen, insbesondere Aluminiumoberflächen, mit einer wässerigen Lösung, welche ein Nickelsalz und ein Fluorid enthält, erzielen lassen.Surprisingly, it was found that these results can be obtained by treating the anodically oxidized and possibly colored metal surfaces, in particular aluminum surfaces, with an aqueous solution, which contains a nickel salt and a fluoride.
Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Nachverdichtung anodisch oxidier ter ungefärbter oder gefärbter Metalloberflächen, insbesondere Aluminiumoberflächen, welches dadurch gekennzeichnet ist, dass die noch nasse Oberfläche bei einer Temperatur unter 30°C mit einer wässerigen Lösung behandelt wird, welche mindestens ein Nickelsalz und mindestens ein Fluorid enthält.The present invention therefore relates to a process for the recompression of anodically oxidized, undyed or colored metal surfaces, in particular aluminum surfaces, which is characterized in that the still wet surface is treated at a temperature below 30 ° C. with an aqueous solution which contains at least one nickel salt and contains at least one fluoride.
Als Nickelsalze eignen sich anorganische Nickelsalze, wie Nickelchlorid, -sulfat, -carbonat, -nitrat, usw., wie auch organische Nickelsalze, wie Nickelacetat und andere. Das Fluorid ist vorzugsweise ein Fluorid eines Alkalimetallsalzes, wie Natriumfluorid, Kalium- fluorid, usw., oder des Ammoniums, z.B. (NH. HF2, oder ein organisches Fluorid.Suitable nickel salts are inorganic nickel salts, such as nickel chloride, sulfate, carbonate, nitrate, etc., and also organic nickel salts, such as nickel acetate and others. The fluoride is preferably a fluoride of an alkali metal salt, such as sodium fluoride, potassium fluoride, etc., or of ammonium, for example (NH. HF 2 , or an organic fluoride.
Vorzugsweise werden die Salze in annähernd stöchiometrischen Mengenverhältnissen von Nickelsalz zu Fluorid eingesetzt, wobei beim Nickelsalz auch das vorhandene Kristallwasser zu berücksichtigen ist. Es können auch grössere oder kleinere Mengen des Nickel- oder Fluoridsalzes verwendet werden, doch sind die Resultate im allgemeinen weniger gut. Die optimale Zugabe an Salzen pro Liter Badflüssigkeit richtet sich nach der jeweils zu behandelnden Oberfläche und kann durch einfache Versuche ermittelt werden. Im allgemeinen beträgt der Salzzustand total (Nickelsalz und Fluorid) etwa 1 bis 20 g/Liter, wobei eine Menge von etwa 10 g/Litern für Aluminiumoberflächen bevorzugt wird.The salts are preferably used in approximately stoichiometric proportions of nickel salt to fluoride, the crystal water present also having to be taken into account in the case of the nickel salt. Larger or smaller amounts of the nickel or fluoride salt can also be used, but the results are generally less good. The optimal addition of salts per liter of bath liquid depends on the surface to be treated and can be determined by simple tests. In general, the total salt state (nickel salt and fluoride) is about 1 to 20 g / liter, with an amount of about 10 g / liter being preferred for aluminum surfaces.
Das pH der Behandlungslösung liegt mit Vorteil im leicht sauren Bereich, z.B. bei 5,5 bis 5,8 und kann mit einer üblichen Säure, z.B. Essigsäure, eingestellt werden.The pH of the treatment solution is advantageously in the slightly acidic range, e.g. at 5.5 to 5.8 and can be mixed with a common acid e.g. Acetic acid.
Die Behandlung erfolgt bei einer Temperatur unter 30°C, vorzugsweise bei Zimmertemperatur, wodurch der Energieverbrauch drastisch herabgesetzt werden kann. Die Berührungszeit der Salzlösung mit der Metalloberfläche ist nicht kritisch. Im allgemeinen beträgt sie mindestens etwa 10 Minuten. Die Behandlung kann durch .Eintauchen in ein Sealbad oder durch Besprühen, Aufpinseln oder auf jede beliebige Art erfolgen. Die behandelte Oberfläche wird im allgemeinen nach der Behandlung mit kaltem Wasser abgespült, doch kann diese Spülung ohne weiteres wegfallen ohne nachteilige Wirkung auf die Qualität der Oberfläche zu haben. Insbesondere, wenn Bäder zur Sealbehandlung verwendet werden, empfiehlt sich der Zusatz eines Konservierungsmittels, wie sie z.B. auch für Färbebäder und andere galvanische Bäder üblich sind, z.B. Formalin, "Preventol" und andere; im allgemeinen genügt ein Zusatz von 0,01 g/Liter. Falls das Konservierungsmittel nicht wasserlöslich ist, kann es in einem mit Wasser mischbaren Lösungsmittel, z.B. einem niederen aliphatischen Alkohol, wie Methanol, Aethanol, Propanol, n- oder iso- Butanol, usw. gelöst der wässerigen Seallösung zugesetzt werden. Ein derartiger Zusatz kann auch für Lösungen zum Aufspritzen, Aufbürsten, usw. empfehlenswert sein, wenn diese Lösungen längere Zeit offen aufbewahrt werden, da sie unter Umständen leicht von Mikroorganismen befallen werden.The treatment takes place at a temperature below 30 ° C, preferably at room temperature, which can drastically reduce energy consumption. The contact time of the salt solution with the metal surface is not critical. Generally it is at least about 10 minutes. Treatment can be by immersion in a seal bath or by spraying, brushing or in any way. The treated surface is generally rinsed off with cold water after the treatment, but this rinse can easily be omitted without having an adverse effect on the quality of the surface. In particular, if baths are used for seal treatment, the addition of a preservative is recommended, as is also common for dye baths and other galvanic baths, for example, formalin, "Preventol" and others; in general an addition of 0.01 g / liter is sufficient. If the preservative is not water-soluble, it can be added to the aqueous seal solution dissolved in a water-miscible solvent, for example a lower aliphatic alcohol, such as methanol, ethanol, propanol, n- or iso-butanol, etc. Such an additive can also be recommended for solutions for spraying, brushing, etc., if these solutions are kept open for a long time, since they can easily be contaminated by microorganisms.
Die Seallösungen können weitere übliche Zusätze, wie Netzmittel und dergleichen, enthalten.The seal solutions can contain other conventional additives, such as wetting agents and the like.
Es ist wichtig, dass die zu behandelnden Oberflächen in noch nassem Zustand der erfindungsgemässen Sealbehandlung unterzogen werden, d.h. praktisch unmittelbar im Anschluss an die Oxidation oder Färbung, bzw. an die letzte Spülung. Sobald die Oxidschicht zu trocken beginnt, ergibt das erfindungsgemässe Verfahren die gewünsch te Verdichtung nicht mehr, selbst wenn die Oberfläche wieder benetzt wird. Dies ist im Gegensatz zu den bisherigen Heisssealverfahren, bei welchen die Oberfläche in trockenem Zustand auch nach längerer Lagerung noch verdichtet werden kann.It is important that the surfaces to be treated are subjected to the seal treatment according to the invention while still wet, ie practically immediately after the oxidation or coloring or after the last rinse. As soon as the oxide layer begins to dry, the method according to the invention gives the desired ones no more compaction, even if the surface is wetted again. This is in contrast to the previous hot sealing processes, in which the surface can still be compacted in the dry state even after long storage.
Das erfindungsgemässe Verfahren ergibt eine hervorragende Korrosionsbeständigkeit und ein glattes, ansprechendes Aussehen der Oberfläche.The method according to the invention results in excellent corrosion resistance and a smooth, attractive appearance of the surface.
Die Verdichtungswirkung hat z.B. bei Aluminium im allgemeinen nach 24 Stunden ihr Maximum erreicht. Die behandelten Gegenstände weisen darin eine bleibende Korrosionsfestigkeit auf und eignen sich für alle üblichen Verwendungszwecke. Hierbei ist keinerlei Ablagerung oder Hydratbildung auf den Oberflächen zu beobachten.The compression effect has e.g. aluminum generally reaches its maximum after 24 hours. The treated objects have a permanent corrosion resistance and are suitable for all common uses. No deposits or hydrate formation are observed on the surfaces.
Der Abtragswert f.ür Aluminiumblech bestimmt nachThe removal rate for aluminum sheet is determined by
ISO 3210, der gemäss der heute geltenden Eurasnorm bei Heissverdichtung bis zu 30 mg/dm2 betragen darf, liegt bei erfindungsgemäss kaltverdichteten Blechen bei etwa 7 bis 10 mg/cm2. Die erhaltenen Abtragswerte sind sowohl bei farblos eloxierten Aluminiumoberflächen wie insbesondere bei z.B. mit elektrolytischeT Metallsalzfärbung gefärbten Aluminiumoberflächen gegenüber denjenigen von heissverdichteten Oberflächen (mit oder ohne Salzzusatz) wesentlich verbessert.ISO 3210, which may be up to 30 mg / dm 2 in hot compression according to the currently applicable Euras standard, is around 7 to 10 mg / cm 2 for cold-compressed sheets according to the invention. The removal values obtained are both compared to those of colorless anodized aluminum surfaces and in particular of aluminum surfaces colored, for example, with electrolytic metal salt staining hot-compressed surfaces (with or without added salt) significantly improved.
Ausser der beträchtlichen Energie-Ersparnis bieten die erfindungsgemäss verwendeten Lösungen den Vorteil, wesentlich weniger umweltbelastend zu sein als die bisherigen, da ihre Lebensdauer praktisch unbeschränkt ist, sie also nicht weggeworfen werden müssen.In addition to the considerable energy savings, the solutions used according to the invention have the advantage of being significantly less polluting than the previous ones, since their service life is practically unlimited, so they do not have to be thrown away.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein handelsfähiges Mittel zur Durchführung des obigen Kaltsealverfahrens. Dieses Mittel ist gekennzeichnet durch einen Gehalt an mindestens einem Nickelsalz und mindestens einem Fluorid der oben beschriebenen Art. Das Mittel kann als trockenes Gemisch, als Paste oder als Konzentrat vorliegen. Vorzugsweise enthält es die Salze in annähernd stöchiometrischem Verhältnis von Nickelsalz . H2O zu Fluorid. Das Mittel kann bereits weitere Zusätze, wie Netzmittel, Konservierungsmittel, usw. enthalten, doch können diese auch getrennt beim Zubereiten der Lösung zugesetzt werden. Das Mittel ist unbeschränkt haltbar und kann z.B. in solcher Dosierungsform abgepackt werden, dass keine Wägung, Messung oder dergleichen beim Ansetzen der Lösung oder bei deren Ergänzung mehr notwendig ist. Beispiel 1Another object of the present invention is a commercial agent for performing the above cold sealing process. This agent is characterized by a content of at least one nickel salt and at least one fluoride of the type described above. The agent can be present as a dry mixture, as a paste or as a concentrate. It preferably contains the salts in an approximately stoichiometric ratio of nickel salt. H 2 O to fluoride. The agent may already contain other additives such as wetting agents, preservatives, etc., but these can also be added separately when preparing the solution. The agent has an unlimited shelf life and can be packaged, for example, in such a dosage form that weighing, measurement or the like is no longer necessary when preparing the solution or supplementing it. example 1
Ein Bad wird hergestellt durch Auflösen von 10 g/Liter eines Gemisches aus 262,9 g Ni(SO4) . 6H2O und 42,0 g NaF in Wasser. Dieser Lösung werden 0,5 g/Liter des Netzmittels "Ekalin F" (Sandoz) und 0,01 g/Liter "Preventol" (Bayer), gelöst in 10 g/Liter Butanol zugesetzt und der pH der Lösung mit Essigsäure auf 5,6 eingestellt.A bath is made by dissolving 10 g / liter of a mixture of 262.9 g of Ni (SO 4 ). 6H 2 O and 42.0 g NaF in water. 0.5 g / liter of the wetting agent "Ekalin F" (Sandoz) and 0.01 g / liter "Preventol" (Bayer), dissolved in 10 g / liter of butanol, are added to this solution and the pH of the solution to 5 with acetic acid. 6 set.
Aluminiumprofile, die auf übliche Art farblos eloxiert und von denen ein Teil zusätzlich mit "Colinal" 3175 gefärbt wurden (Schichtdicke 24 μ), wurden unmittelbar nach Verlassen des letzten Spülbades in das obige Bad, das eine Temperatur von etwa 25°C aufwies, verbracht und 15 Minuten darin belassen. Nach 24 Stunden betrug der Abtragswert bei den farblosen Oberflächen 6,9 bei den gefärbten Oberflächen 9,4 mg/dm2.Aluminum profiles, which were colorless anodized in the usual way and some of which were additionally colored with "Colinal" 3175 (layer thickness 24 μ), were placed in the above bath, which had a temperature of approximately 25 ° C., immediately after leaving the last rinsing bath and leave it there for 15 minutes. After 24 hours, the erosion value for the colorless surfaces was 6.9 for the colored surfaces 9.4 mg / dm 2 .
Beispiel 2Example 2
Zum Vergleich wurden gleiche farblos eloxierteFor comparison, the same colorless anodized ones
Profile mit einer Schichtdicke von 24 μ der üblichenProfiles with a layer thickness of 24 μ the usual
Heissverdichtung unterworfen, wobei Abtragswerte von 16,4 mg/dm2 erhalten wurden. Gleiche farblos eloxierte, unverdichtete Profile ergaben nach Verdichtung wie in Beispiel 1 beschrieben, einen Abtrag von 14,4 mg/dm2. Subjected to hot compression, whereby removal values of 16.4 mg / dm 2 were obtained. The same colorless anodized, undensified profiles resulted in a removal of 14.4 mg / dm 2 after compression as described in Example 1.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Verfahren zur Nachverdichtung der Oberfläche von anodisch oxidierten, ungefärbten oder gefärbten Metallen, insbesondere Aluminium, dadurch gekennzeichnet, dass man die noch nasse Oberfläche bei einer Temperatur unter 30 °C mit einer wässerigen Lösung in Berührung bringt, welche mindestens ein Nickelsalz und mindestens ein Fluorid enthält.1. A method for the densification of the surface of anodically oxidized, undyed or colored metals, in particular aluminum, characterized in that the still wet surface is brought into contact with an aqueous solution which has at least one nickel salt and at least one at a temperature below 30 ° C. Contains fluoride.
2. Verfahren nach Patentanspruch 1, dadurch gekennzeichnet, dass das Kation des Fluorides ein Alkali, vorzugsweise Natrium oder Kalium, Ammonium oder ein einwertiger organischer Rest ist.2. The method according to claim 1, characterized in that the cation of the fluoride is an alkali, preferably sodium or potassium, ammonium or a monovalent organic radical.
3. Verfahren nach Patentanspruch 1 oder 2, dadurch gekennzeichnet, dass die Lösung ein pH im leicht sauren Bereich aufweist, z.B. zwischen 5,5 und 5,8.3. The method according to claim 1 or 2, characterized in that the solution has a pH in the slightly acidic range, e.g. between 5.5 and 5.8.
4. Verfahren nach einem der Patentansprüche 1 bis 3, dadurch gekennzeichnet, dass die Salze in annähernd stöchiometrischer Menge von Nickelsalz, ein schliesslich Kristallwasser, zu Fluorid verwendet werden.4. The method according to any one of claims 1 to 3, characterized in that the salts in an approximately stoichiometric amount of nickel salt finally crystal water, can be used to fluoride.
5. Verfahren nach einem der Patentansprüche 1 bis 4, dadurch gekennzeichnet, dass der Lösung ein Konservierungsmittel und gegebenenfalls weitere Hilfsmittel, z.B. ein Netzmittel, zugesetzt werden.5. The method according to any one of claims 1 to 4, characterized in that the solution is a preservative and optionally other auxiliaries, e.g. a wetting agent.
6. Mittel zur Durchführung des Verfahrens nach Patentanspruch 1, dadurch gekennzeichnet, dass es mindestens ein Nickelsalz und mindestens ein Fluorid enthält.6. Means for performing the method according to claim 1, characterized in that it contains at least one nickel salt and at least one fluoride.
7. Mittel nach Patentanspruch 6, dadurch gekennzeichnet, dass das Fluorid ein Alkalimetallfluorid, ein Ammoniumfluorid oder ein Fluorid mit organischem Kation ist.7. Composition according to claim 6, characterized in that the fluoride is an alkali metal fluoride, an ammonium fluoride or a fluoride with an organic cation.
8. Mittel nach Patentanspruch 6 oder 7, dadurch gekennzeichnet, dass es die Salze in annähernd stöchiometrischem Verhältnis von Nickelsalz, einschliesslich Kristallwasser zu Fluorid enthält.8. Composition according to claim 6 or 7, characterized in that it contains the salts in an approximately stoichiometric ratio of nickel salt, including water of crystallization to fluoride.
9. Mittel, nach einem der Patentansprüche 6 bis 8, dadurch gekennzeichnet, dass es weitere Hilfsmittel, wie Netzmittel, Konservierungsmittel, usw., enthält.9. Agent, according to one of claims 6 to 8, characterized in that it contains other auxiliaries, such as wetting agents, preservatives, etc.
10. Aluminiumgegenstand, dadurch gekennzeichnet, dass seine Oberfläche nach dem Verfahren gemäss Patentanspruch 1 behandelt wurde. 10. aluminum object, characterized in that its surface was treated by the method according to claim 1.
PCT/CH1983/000100 1982-09-03 1983-09-01 Recompression process WO1984000982A1 (en)

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AT83902690T ATE31198T1 (en) 1982-09-03 1983-09-01 RECOMPRESSION PROCESS.
AU18861/83A AU1886183A (en) 1982-09-03 1983-09-01 Nachverdichtungsverfahren

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FR2543580A1 (en) * 1983-03-28 1984-10-05 Boston Spa METHOD AND BATH FOR FIXING ALUMINUM AND ALUMINUM ALLOYS FOLLOWING ANODIZATION TREATMENT
EP0171799A2 (en) * 1984-08-16 1986-02-19 HENKEL CORPORATION (a Delaware corp.) Sealant compositions for anodized aluminum
EP0193964A1 (en) * 1985-03-08 1986-09-10 HENKEL CORPORATION (a Delaware corp.) Low temperature seal for anodized aluminum surfaces
DE3641766A1 (en) * 1986-12-06 1988-06-09 Erbsloeh Julius & August Method of producing light-fast and weather-resistant anodised and coloured layers on aluminium and aluminium alloys
EP1087038A1 (en) * 1999-09-23 2001-03-28 Clariant International Ltd. Process for dyeing oxide layers on aluminum

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FR2543580A1 (en) * 1983-03-28 1984-10-05 Boston Spa METHOD AND BATH FOR FIXING ALUMINUM AND ALUMINUM ALLOYS FOLLOWING ANODIZATION TREATMENT
EP0171799A2 (en) * 1984-08-16 1986-02-19 HENKEL CORPORATION (a Delaware corp.) Sealant compositions for anodized aluminum
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EP0193964A1 (en) * 1985-03-08 1986-09-10 HENKEL CORPORATION (a Delaware corp.) Low temperature seal for anodized aluminum surfaces
DE3641766A1 (en) * 1986-12-06 1988-06-09 Erbsloeh Julius & August Method of producing light-fast and weather-resistant anodised and coloured layers on aluminium and aluminium alloys
EP1087038A1 (en) * 1999-09-23 2001-03-28 Clariant International Ltd. Process for dyeing oxide layers on aluminum
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US4648911A (en) 1987-03-10
DE3374791D1 (en) 1988-01-14
EP0118480B1 (en) 1987-12-02

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